Durable press textile materials by anhydrous solvent finishing process

ABSTRACT

ANHYDROUS SOLVENT FINISHING PROCESSES TO IMPART DURABLE PRESS PROPERTIES TO CELLULOSIC TEXTILE MATERIALS, E.G., FLAT GOODS OR FINISHED GARMENTS MADE OF 100% COTTON FIBER OR COTTON/SYNTHETIC FIBER BLENDS, INVOLVE IMPREGNATING TEXTILE MATERIAL WITH AN ANHYDROUS MIXTURE OF METHYLOLATED CARBAMATE, ORGANIC SOLVENT AND ORGANIC AMINOPLAST CROSS-LINKING CATALYST, REMOVING SOLVENT, EXPOSING THE SOLVENT-DEPLETED TEXTILE MATERIAL TO WATER VAPOR TO GIVE A MOISTURE REGAIN OF 8 TO 15% AND THEN HEAT CURING AT ABOUT 120* TO 200*C. THE ANHYDROUS ORGANIC SOLVENT MIXTURE MAY INCUDE A SOLUBLE FIRE-RETARDANT SO THAT THE RESULTING FABRIC ACQUIRES BOTH DURABLE PRESS AND FIRE RETARDANCY PROPERTIES.

States Patent" Office ABSTRACT on THE DISCLOSURE ='Anhydrous solvent finishing processes to impart durable press properties to cellulosic textile materials, e.g., fiat goods' or finished garments made of 100% cotton fiber or cotton/synthetic fiber blends, involve impregnating textile material with an anhydrous mixture of methylolated'carbamate, organic solvent and organic aminoplast cross-linking catalyst, removing solvent, exposing the solvent-depleted textile material to water vapor to give a moisture regain of 8 to 15% and then heat curing at about 120 to 200 C. The anhydrous organic solvent mixture may include a soluble fire-retardant so that the resulting fabric acquires both durable press and fire retardancy properties.

BACKGROUND OF THE INVENTION Field of the Invention The invention relates to the finishing of fabrics and other textile materials made of cellulosic fibers to impart durable press qualities thereto. More particularly, it concerns anhydrous solvent finishing methods for cellulosic textile materials capable of creating high durable press ratings for the textile material and, in some embodiments, simultaneously also creating good fire-retardancy.

Description of the Prior Art Textile articles that can be laundered or cleansed and still. maintain an unwrinkled, finished appearance are much in demand. At the present time, a major portion of garments, sheets, pillow cases and other white goods and related textile articles used by people in daily activities and in their households are of this type. A variety of terms have been used to refer to textile materials which can be laundered or cleansed without requiring a substantial amount or ironing or pressing in order for the textile article to have a sufiiciently good appearance to be put right back into use after the laundering or cleansing. The term wash-wear has been used extensively to describe such textile materials. They have also been referred to as durable press articles, particularly in describing finished garments. Other terms have also been employed, some being more extensively used in scientific fields while others are more popular with laymen. The present invention relates to that class of textile materials which resist creasing o'rother alteration in appearance when subjected to repeated launderings or cleansings sufficiently that they may be returned to their intended use or service without requiiing ironing or pressing, except possibly so-called touch-up ironing to provide a completely renewed appearance. This type of textile material which will, for the sake of consistency and brevity, be referred to hereinafter as a durable press textile material.

Durable press properties in textile articles can be obtained in a variety of ways. Some fibers and fabrics exhibit muchlesstendency towards creasing or developing an unacceptable appearance than do other fibers or fabrics. For example; knit goods made of certain synthetic fibers require less attention to restore satisfactory appearance than do woven fabrics made of natural fibers. A principal method'ofimparting durable press properties to textile articles Patented Sept. 10, 1974 is by treating a fabric or a finished garment with some form of crease-proofing agent.

An enormous amount of research and development work has been devoted to the improvement of durable press textile articles while mitigating adverse eifects such as loss of tensile strength or abrasion resistance, lowering the cost of production and manufacture or the like.,1n large measure, this has involved investigation of numerous types of crease-proofing agents, methods of treating textiles with them, catalyst systems used in such methods and the like. Ureaformaldehyde resins, melamine-formaldehyde resins and a multitude of other nitrogen containing resins or their precursors, broadly referred to as amino plasts, constitute one of the major types of materials used as crease-proofing agents for cellulosic textile materials. They are applied almost exclusively to fibers and fabrics from aqueous systems, i.e., solutions or dispersions of the agents in water or liquids containing a substantial amount of water. In addition to the durability problems, i.e., re-

duction in abrasion resistance and tensile strength, many of the agents of this class also create a chlorine-retention problem, i.e., accumulation of chlorine in the fabric following the application of chlorine containing bleaches due to the presence in the fabric of a crease-proofing agent. This latter deficiency has in large measure been eliminated by the use of monocyclic urea derivatives as agents for providing the desired durable press properties (see US. 2,373,135).

One class of chemical compounds which have been found to provide relatively high durable press values with relatively low detrimental side effects are methylolated carbamates (see US. 3,144,299). These have been applied to fibers of fabrics from aqueous systems and special catalysts have been developed for use in such operations (see US. 3,369,585). Modifications of such operations have included use of special combinations of carbamate treating agents (see US. 3,548,427). The utilization of carbamates in this manner has become so extensive that improved procedures for producing and manufacturing methylolated carbamates have been developed (see US. 3,391,181). The present invention concerns improved procedures for imparting durable press properties to cellulosic textile materials using methylolated carbamates.

Non-aqueous systems have been used to a limited extent for the treatment of textile materials with crease-proofing agents. For example, solutions of treating agents in organic solvents may be employed for impregnation of textile materials where the agent is either completely insoluble in water or will decompose if brought into contact with water. In such cases, the organic solvent solution can be employed to place the treating agent in or upon the fabric after which an aqueous-treating system may be applied (see US. 3,508,860). In other cases, non-aqueous solutions of treating agents in organic solvents that have a swelling action on fibers comparable to water have been used to apply treating agents to fibers and fabrics (see US. 2,161,805).

The use of aminoplasts as crease-proofing agents depends, at least in part, in a cross-linking reaction between hydroxyl groups in the cellulosic fibers of the textile material and methylol or equivalent groups in the amino; plasts. Many aminoplasts can also undergo condensation polymerization creating resinous materials within the fiber or fabric which to some extent contribute to durable press properties imparted to the textile material. How

ever, a large number of the eifec'tive nitrogen containing and their crease-proofing characteristics are due to a cross-linking action upon the cellulosic fibers of the textile materials. In contrast, there are operations for producing durable press fabrics in which fabrics are tf"atcf"with fesin' forming substances that are not re active with the cellulosic fibers so that crease-proofing effects .are due entirely to the formation in the fabric off resinous "materials. Unsaturated organic compounds, e.g., acrylic acid esters, capable of I undergoing freer adlical type polymerization havebeenused for this purposeI'S uch polymerized unsaturated compounds are usually Wat er-insol uble'and solutionsof such compounds in orgahicsol vents arefrequently used to apply an unsatur'ated'compound' to a textile material so that it may be polymerized in'situ upon thejtextile material (see U.S. 2,071,419)? OBJECTS A principal object of this invention is the provision of new improvements in the production of durable press textile materials. Further objects include the provision of: p (1) New methods for treating cellulosic textile materials with non-aqueous crease-proofing compositions to impart durable press properties.

(2) New finishing processes for cellulosic textile materials to impart durable press properties which may be applied to 100% cotton fiber fabrics.

(3) New durable press treatments for cellulosic textile materials that can simultaneously impart fire-retardancy to the textile material.

(4) New forms of cellulosic textile materials that exhibit high durable press ratings along with satisfactory tensile strength and abrasion resistance.

(5) New anhydrous, organic solvent compositions for use in the finishing of celluiosic textile materials to impart durable press properties.

Other objects and further scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however. that the detailed description, while indicating preferred embodiments of the invention, is given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. It should also be understood the foregoing abstract of the disclosure is for the purpose of providing a non-legal brief statement to serve as a searching-scanning tool for scientists, engineers and researchers and is not intended to limit the scope of the invention as disclosed herein nor is it intended it should be used in interpreting or in any way limiting the scope or fair meaning of the appended claims.

SUMMARY OF THE INVENTION solvent- 'rnedia', there can be substantial improvement in,

the overall properties of the treated material as contrastedfto results obtained using aqueous systems. Further, the ciuring of the fabric to produce reaction between the methylolated carbamate and cellulosic fibers of the textile material to generate the durable press effect can be accomplished in very short time so that the new'operations ,befllsed 'in mills for normally fast continuous proce s g.

p ss' lulosic' textile materials in accordance with the in ention involve the following steps: l roviding asubstantially anhydrous mixture cornprisinggthe. following: (a.)' methylolated carbatnate,

ta briefly, processes for the production of durable ated carbamate used in the anhydrous sylstern.

v ing cross-linking catalytic efifect onaminoplastsare n (b) organic solvent having a b lng point be e "50 and 200C,

(c) organic aminoplast cross-linking catalyst soluble in said organic solvent,

(B) Impregnating cellulosictextile material with said anhydrous mixture to providedn' tl'ieitextfle .tnat'er l1; 1 tween about 1 and 10% of 'said'methylola-te based upon the dry weight of saidtext;ile rna"ter1al (C) Removing organic solvent from the textile material resulting'from step'B,

D) Exposing the solvent-depleted t I step C to water vapor to create therein a of between about 8 to 15% in the cellulosic fibers of the fabric. 1 T f".

(E) Heating the textile material C esul tingifrom step D at a temperature between about and-2.009 W p a time between about 1 and 30minutes sufficient to pro duce an increased durable press rating in sai d t xtil ma terial. i

The anhydrous solvent..finishing processes-of h ing durable press propertiesin cellulosjcttextilemate However, particularly useful results have been obtained rg accordance with the invention using methylolated; car bamates of the formula: 5

0 CHZOH R is 1 to 4 carbon atomalkyl,

R is 1 to 20 carbon atom alkylene,

R is H or R and" R is CH OH when R1 is Xo'r 50H or R R is Y. r A preferred class of the methylolated carbarnates those having the following formulaz wherein: I

R is l to 4 carbon atomalkyl, and R is 1 to 4 carbon atom allrylene' durable press producingragent L 'As to the catalyst used to pro ,ote cross-l g h tween the methylolatedcarbamate and theeellulosie fi bers, a variety of organic solvent ,solublecomppnn s.hav-

and can be used. Advantageously, from among these a catalyst will be selected which does not adver elyxaffegg fabric strength, color or other desiredqualities. By way of example, p-toluene sulfonyl chloride, has been found particularlyuseful. Preferred catalysts are those selected from the group consistingof haloaryllacetones, halimides andarylsulfonyl halides. V p; p

Success of the inventionis, in part, further due to the discovery that durable fire-retardant properties can be produced in .cellulosic textile materials simultaneously with :durable press properties using the same anhydrous solvent systems as outlined above relative to the durable press agent. Halogenated hydrocarbyl phosphates constitufe a preferred type (or fire-iretartlant agent for use in these new textile treatments. However, a variety of other fire-retardants may be employed as disclosed hereinafter and also in copending applicationSN. 292,145, filed Sept. 25, 1972 t he disclosure of whichis incorporated herein by reference.

- DESCRIPTION OF PREFERRED EMBODIMENTS The'following details of operations in accordance with the invention and reported data illustrate the further principles of practice of the invention to those skilled in the art. In these'examples and through the remaining specification and claims, all parts and percentages are by weight unless otherwise specified.

Example I A' section of 100% cotton broadcloth fabric was immersed in the resulting solution until it was thoroughly impregnated. It was then pad-squeezed to a wet pick-up of 80%, after which it was dried at room temperature (20-Z5 'C.) for minutes resulting in substantially complete evaporation of the trichloroethane. Next the fabric section was wet steamed to a moisture regain of 815 %s and then immediately subjected to a hot air cure c'ycle of 1.5 minutes at 170 C. After being removed from the hot air oven, the fabric section was conditioned to ambient temperature and humidity and then subjected to several standard fabric testing procedures. This produced the following data:

Crease Recovery (AATCC No. 66Recovery Angle Method) (warp and filling) :280+ Durable Press Rating (AATCC No. 124--Durable Press Replica) after 50 home launderings=3.8-4.2

Example II As an Example I, a clear solution was made of the following ingredients: 1

i Parts N,N-dimethylol ethyl carbamate 125 Benzene sulfonyl chloride 10 n-Propanol 10 Methoxyethanol Perchloroethylene 6 Example III As in Example I, a clear solution was made of the following ingredients:

Parts N,N-dimethylol tetrahydrofurfural carbamate 12 5 p-Toluene sulfonyl chloride 10 n-Propanol 10 Trichloroethylene '855 A 50/50 polyester/cotton broadcloth was impregnated by pressure spray application to produce a wet pick-up of 65%. The fabric was then passed over low pressure'(30 40 p.s.i.g.) steam cans to produce solvent evaporation and dry the fabric. This was then followed by light steaming to product a moisture regain of 8-15 in the cellulose fibers of the fabric. Finally, the fabric was cured for 1 minute at 160-165 C. The ambient conditioned fabric when tested produced the following data:

Crease Recovery=280 Durable Press Rating=4.04.2 (50 launderings) Example IV As in Example I, a clear solution was made of the following ingredients:

Parts N,N-dimethylol-Z-methoxyethyl carbamate p-Toluene sulfonyl chloride 10 Tris (2,3-dibromopropyl) phosphate 250 Methoxy methyl melamine 50 1,1,l,-trichloroethane 565 A 100% cotton broadcloth was impregnated with the solution and the pad-squeezed to a wet pick-up of 80%. The fabric was air dried at room temperature for 10 minutes and then lightly steamed to produce a moisture regain of l015%. Finally, the fabric was cured for l minute at 160-165 C. The ambient conditioned fabric when tested produced the following data:

Crease Recovery:278" Durable "Press Rating: 4.0 (one laundering) Durable Press Rating=3.84.0 (50 launderings) Vertical Char (AATCC No. 341969)=4.5" (one laundering) no flame or after glow Vertical Char=7-8" (50 launderings) no flame or after glow Example V As in Example I, a clear solution was made of the following ingredients:

Parts N,N-dimethylol-2-methoxyethyl carbamate p-Toluene sulfonyl chloride 10 Tris (2,3-dibromopropyl) phosphate 200 Methoxy methyl melamine 50 1,1,1-trichloroethane 615 A 100% viscose rayon prepared fabric impregnated with the solution to a wet pick-upof 70%. The fabric was dried by solvent evaporation for 10 minutes at room temperature and then lightly steamed to a moisture regain of 815%. Finally the fabric was hot air cured for l minute at l65 C. The ambient conditioned fabric when tested produced the following data:

Crease Recovery=265 Durable Press Rating=3.8 (one laundering) 1 Durable Press Rating=3.5 (50 launderings) Vertical Char=4.5" (one laundering) no flame or after glow Vertical Char==7.0 (50 launderings) no flame or after glow i Example VI 'hs mnr'amue r;- a"cle'a'r "solution was made bf thfollowing ingredients: L

Parts ,N -dimethylol 2-rnethoxyethyl carbamate 125 fpFToluene sulfoh'yl chloride" i 1'0 Iris '(2,3dibromopropyl) phosphate 3 50 Methoxy methyl melamine A 50 1,1,1-trichoroethane 465 Crease Recovery=285 Durable Press Rating:4.5 (one laundering) Durable Press Rating=4.5 (30 launderings) Vertical Char:5.5 (one laundering) Vertical Char=8-9 (30 launderings) DISCUSSION OF DETAILS The new anhydrous solution methods for treatment of cellulosic textile articles to obtain durable press effects are contemplated for use with all methylolated carbamates known to be useful as crease-proofing agents for cellulosic fabrics. Such reagents are discussed in numerous publications and patents, e.-g., see US. Pats. 3,219,686; 3,369,858; 3,391,181; 3,548,427 and 3,553,254 the disclosures of which are incorporated herein by reference. N,N-dimethylol alkoxy alkyl carbamates as hereinbefore defined are particularly useful, e.g., N,'N-dimethylol2- methoxyethyl carbamate. Specific examples of other carbamates preferred for use in the new methods include the N,N-dimethylol derivatives of the following carbamates:

ethyl carbamate octadecyl carbamate tetrahydrofurfural carbamatecyclohexyl carbamate allyl carbamate n-propyl carbamate 2-ethyl hexyl carbamate isopropyl carbamate 27chloroethyl carbamate hydroxyethyl carbamate- 3-bromopropyl carbamate phenyl carbamate 3-ethoxypropyl carbamate p-chlorophenyl carbamate 6-methoxyhexyl carbamate p-tolyl carbamate Additional examples of specific carbamates useful in the new operations include:

N,N'-dimethylol ethylene bis (ethyl carbamate) N,N-dimethylol butane-1,3-diol dicarbamate N,N-dimethylol diethylene glycol dicarbamate polymethylol pentaerythritol tetracarbamate N,N,N"-trimethylol glycerol tricarbamate j! polymethylol sorbltal hexakis (methyl carbamate) dimethylol-2,4-pentane-1,5-diol dicarbamate,

ltTlie halogenatdhydrocarbons having a boiling point between about 20200 C. and espe'cially between about are afpreferred class of anhydrous organic solvents for use in the new DP fabric treatments, e .gl; 1,1,1-trichloroethane, butyl bromide, perchloroethylene, trichloroethylene, ethylene chloride, ethylene. bromide", 1,1,2 trichloro- 1,2,2.- trifiuoroethane, 1,1,1 trichloro- 2,2,2 trifiuoroethanq, methallyl chloride and .1,1-di chlqroethanewother anhydrous. organic solvents of similar boiling range may, however, be used including hexane, pentene-l methyl ethyl.lgetone,;.isopropyl acetate, ethyl acetate, isopropyl ether, ethyl formate, neohexane,dioxolane, cyclohexane, cyclopentane, benzene, acetone and the a like. Minutes" OftWO' arm-ore anhydrous or ganrc soiveuts may' also'b'e usedwithdv'antage, partijcula'rlywh is desired to control evaporation ordrying 'r-ate" of th treatment solution from the impregnated tex le te'r'ia A wide selection of aminoplast'catalysts hydrous organic solvents are' available for' u DP treatments. 'Advantagously; ohselctfshoh' V lyst that will not 'stairi or discolor the-fabric, e as ex sive tenderingor' present safety or pollutiortproble Aromatic sulfonyl halides liave'been foundto be particularly useful, e.g.-, p-tolu'ris'ultonylicliloride beniene fonyl chloride,2-chloi 4-ethylp'h' yl "sillf' 2-butyl-4-methoxyphen'ylfsulfonyl chloridej ben n fonyl bromide and thef'likefThe catalyst should be soluble at least'jtof the exten a organic solventhereinbfore described. Advantageou y, compounds used as the catalyst are acidic or react with water to form an acidicv product. Additionalpreferred classes of compounds touse as catalysts ,;in clude. halogenated aromatic lact'ones, e chlorophthalide, bir omo; phthalide, iodophthalide, etc; and haloimides, e.g chlorosuccimide, N-brioinofl dibroino ,suc cimid chloro teraconimide, N chIQr'O hth'aIimidef, and; the

The amount of catalyst use'dwill depend, inpa rt, uponte particular carbamate reagent'used, the temperature for curing and similar factors. Generally, the fabric treating solution will comprise 0.1,.to, 10%of.the catalyst and especially 0.1 to 5%. .-,g, I 5:} Two major components of the anhydrous textile-treat; ing solution of the invention are methylolated carbamate and organic solvent. Such solutions may 'contain l;tj'o,50% methylolated carbamate or carbamate mixtures and-pare ticularly 5 to 20%, catalyst inamount as aforesaid-.:and the remainder organic solvent, e.g.,. 40 to; 98%.- solventi Advantageous solutions comprise 5 ,to'.20%..;ca t=bam ate component, 0.1 to 5% catalyst and the remainder organic bon solvent of which at least90%' is halogenated hi or mixture, particularly halogenatejd hydro'ca ons to3carbon atoms. 4

The organic solvent"component of the treating sol tion may contain up to about 10%, e.g., ,1 5% ,;of or' hydroxy compound to improve solubility of therai bamate component. Alkanols of, 1 6 carbonatoms, e'.g. ethanol; isopropanol, n-butanol', trt, -bmane1,,met anol, haxanol, etc. or alkoxyalkanols of "3-8 carbon atoms, efgf, rrletho ethanol, ethoxy ethanol, oxy b'utanol, M etc. are useful for this hydroxy compounds may advantageously the amounts indicated. v 7

As illustrated by Examples IV to VI,-'=a thir d-major" component of the new'anhydrou'streating solution-maybe a fire-retardant. Such componentwhen'izsed' mayco'nl prise up to 60% of the treatingsolutiorfiand'may, iii part, serve as a solvent vehicle for the carbamate component. Any anhydrous organic compounds known to be useful as fire-retardants are contemplated for use .as c mponents of the treating solutions, e.g., see Chem.- and -Eng.'News, Oct. 18, 1971, p. 16-19. Organic chlorine compounds, bromine compounds, nitrogen compounds and compounds having flame-proofing qualities I they are non-reactive'with the carbamate inpo v Advantageously, the treating solutions of theiinve n, when'fire retardancy as well as DP effects aredes'ired w ll contain 5 to 40% of the flame-proofingagentfPreferred solutions of-this type willcomprise 5, to 20% carbamate component, 10 to 307"fi retardant 1 05% catalyst, 20 to ,.anhydro'us rga nicisolven andfup of an auxiliary reagent I f I M .A'u'xil-ia ry reagents of 'var'ious types erb inr a the treating solutions,advantageously,in amounts'betwe en 0.110 20% and particularly bet ween 0.5;15 7 especially;

1-1 0%. Such auxiliary reagents include dyes; thermo setting resins, e.g., methyl and but-yl' ethers ofadirnethylol derivatives of triazones," ethylene qurea tmelaminfi, propyll-i ene urea, etc; mildew-proofing agent; sanitizing agents;

softening agents, plasticizers; hand-builders and the like. The DP treatments of the ,invention are.usable :with all varieties of cellulosic textile materials. Theterm .fcellu losic textile material as used herein is intended to mean any woven, knit or non-woven fabric as well as garments, bed-clothes, furniture coverings or any other textile material made in whole or in part of cellulosic fibers. Cellulosic fibers include cotton, linen, viscose rayon, high modulus rayon (polynosic). These may be blended in yarns with synthetic fibers, e.g., nylon, polyester, polyolefin and other fibers or filaments or the textile materials may comprise mixed weaves or knits of cellulosicyarns or filaments and synthetic yarns or filaments. A particular advantage of the invention is the ability of the new operations to impart DP efiects to 100% cotton textile materials without undue loss of tensile strength and abrasion resistance.

The anhydrous treating solutions of the invention may be applied in a variety of ways. Dipping and padding, well known in the art, can be used. Additional methods include spraying, roller coating, float coating and the like. However, if enclosed equipment is not used, loss of solvent to the atmoshpere can be costly and/or present ecological problems. Equipment is commercially available to preform the application of organic solvent treating solutions without loss of solvent to textile material, e.g., see Textile Industries, October 1966, pp. 288-9, 291, 295, 299, 339 and 397.

The amount of solution applied will depend upon the type of farbric, e.g., whether woven or knit and its weight, the degree of DP effect desired, the concentration of carbamate in the solution and similar factors. Under preferred conditions, the amount of solution relative to textile material will be selected to provide in the textile material between about l20%, especially 1-10%, of carbamate component based upon the dry weight of the cellulosic textile material. Typically, this will involve a wet pick-up of treating solution between about 50-150% based upon the dry weight of the textile material.

Following the application of the anhydrous treating solution, the volatile components of the solution are removed, e.g., by evaporation. Passage of the textile material through drying oven-s, through infra-red ovens or in any other suitable manner may be used. The evaporated organic solvent is removed and recovered with available solvent handling systems. As a less desirable alternative, the impregnated textile material may be permitted simply to air dry at ambient conditions.

The removal of the organic solvent from the textile material leaves a moisture and solvent depleted fabric. At this point in the new operations, the solvent depleted fabric is exposing to water vapor to create therein a moisture regain in the cellulosic portion of the fabric of between about 8 and For 100% cotton, this will mean a total moisture regain of 815% while a 50% cotton/50% polyester fabric would involve a total moisture regain of 4-7.5 Advantageously, this is accomplished by steaming of the textile material. Exposure to high humidity at room temperature or other moisture regain techniques can, however, be used. As an alternative, the moisture regain step may be applied before the solution application or before the solvent evaporation steps. However, more pronounced DP effects are obtained when the moisture regain step is applied after the solvent evaporation. This also improves solvent recovery operations. The moisture regain step appears to be necessary to the success of the new methods, at least in part, to produce ionization of the acidic catalyst to produce the curing of the impregnated textile material.

The textile material ultimately is subjected to a heat curing step to produce cross-linking of the cellulosic fiber components with the methylolated carbamate. This heat curing may proceed immediately after the combination of solution application and moisture regain. Alternatively, a delay cure procedure may be used. In any event, heat to curing equivalent to 1-30 minutes at 120 to 200 C,;i s used to sufliciently produce an increased durable press rating in the textile material as compared to untreated textile material. t

CONCLUSION New anhydrous organic solventprocedures have been described for treatment of "cellulosic textile-materials to obtain durable "presseffects. These new techniques en hance, rather than diminishtheoverall properties of" the fabric. Moreover; the procedures may be operatedto attain durable fire-rtardancyl as well' as" DP enacts: Further; the curing ofthe" textile material can be effected in avery short time so'tha't the"newoperations are usable in textile mills requiring fast, continuous processing of fabrics.

The embodiments of the invention in which are exclusive property or right is claimed are defined as follows:

1. A process for the production of durable press cellulosic textile materials which comprises:

(A) providing a substantially anhydrous mixture comprising the following ingredients in the percentages by weight indicated:

(a) 5 to 20% methylolated carbamate (b) 0.1 to 5% organic aminoplast cross-linking catalyst selected from the group consisting of haloaryllactones, haloimides and aryl sulfonyl halides,

(c) remainder being organic solvent having a boiling point between about 50 and 200 C. comprising at least of halogenated hydrocarbon containing 2 to 6 carbon atoms,

(B) impregnating cellulosic textile material with said anhydrous mixture to provide in the textile material between about 1 and 10% of said methylolated carbamate based upon the dry weight of said textile material,

(C) drying said textile material resulting from step B by evaporation of said organic solvent,

(D) exposing the dried textile material from step C to water vapor to create therein a moisture regain of between about 8 and 15%,

(E) heating the textile material at a temperature between about and 200 C. for a time between about 1 and 30 minutes sufficient to produce an increased durable press rating in said textile material.

2. The process of claim 1 wherein said methylolated carbamate has the formula:

R is 1 to 4 carbon atom alkyl, R is l to 20 carbon atom alkylene, R4 is -H 01' R2, and R is -CH OH when R is X or CH OH or R when R1 is Y- 3. The process of claim 1 wherein said methylolated carbamate has the formula:

0 canon no- -N 7 R2 2 R is 1 to 4 carbon atom al lg yl and;; R is 1 to fl carbon atom alkylene.

on mi gli 9 fif The process of claim 1 wherein said catalyst isa monocyclic aryl sulfonyl chloride.

7. The process of claim 1 wherein said catalyst is pto'uene sulfonyl chloride.

8. The process .ofclaim 1 wherein step D is preformed by steaming the textile material.

9. The process of claim 1 wherein said anhydrous mixture contains a fire-retardant soluble in said, organic solvent.

. .10. The process of claim 1.wherein said step B is preformed by immersing the textile material in a bath of said anhydrous mixture and .then it is pad-squeezed to a wet pick-up of between about 50 to 150% of said mixr 12 are based upon" 'theidry' weight of'the textile material. -i1"1.-Cellulo'si c textile mate'rial producd by the process oflainii l'haying a durabl'e' p'i'ess rating ofla't least 3.51

References 'Cited 1 I UN TED a s S A PAT T 3,617,194 7 11/1971 7 Bannister et al. 8-.187 X 3,611,195; ll/1971 Moyse et a]. s,v ,1s2 3,565,846. 2/1971 End ers 6t al. 117 ;139.4.x -3.,.39,1,1s1 7/1968 566611611 r s 1,s7 X

.3548,4 1, 12/1f97 ...c6 et a1.-.. 8.187-

" FOREIGN PATENTS 9/1970 GreatBritain. a

OTHER REFERENCES, Prick et al., Textile bulletin, November 1968, pp. 3 2 Reeves et al., article in Textile Chemist and Colorist;

Aug. 13, 1969, vol. 1, No.17, pp. 365 369.

HERBERT B. GUYNN; Primary Examiner U.S. Cl. X.R.

l17136, 139.4; 260 33.8IR

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. I 3,834,871 Dated September 10, 1974 Inventor(3) J inimy M. Thompson It is certified that error appears in the abore-identified patent and that said Letters Patentare hereby corrected as shown below:

column 1, i 47, "or", first occurrence, should be of Column 2, line 59, "in", second occurrence, should be to Column 3, line 36, the period after "however" should be a comma;

Column 5', line 4,"haloaryllacetones" should be --haloaryllactones-7" l m lih" ,11'srhem eqysle exyrl f .shenLLbe cyclohexyl carbamete Column 9, line 23, "atmoshpere" should be --atomsphere-;

Column 10, betweenlines 15 and 16, insert the heading -Claims--,--;

Column 1O,v line 16, "are" should be --an--.

Signed and sealed this 24th day of December 1974.

. (SEAL) Attest;

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents F ORM PO-105O (10-69) USCOMM-DC OOB'IS-PUQ U. 5. GOVERNMENT HUNTING OFFICE l9" 0-."6-3, 

